WO2017060352A1 - Procédé pour le traitement d'eaux usées contenant une matrice organique résultant de la synthèse de zéolite - Google Patents

Procédé pour le traitement d'eaux usées contenant une matrice organique résultant de la synthèse de zéolite Download PDF

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Publication number
WO2017060352A1
WO2017060352A1 PCT/EP2016/073878 EP2016073878W WO2017060352A1 WO 2017060352 A1 WO2017060352 A1 WO 2017060352A1 EP 2016073878 W EP2016073878 W EP 2016073878W WO 2017060352 A1 WO2017060352 A1 WO 2017060352A1
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Prior art keywords
waste water
adsorbent material
water stream
nonionic adsorbent
range
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PCT/EP2016/073878
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English (en)
Inventor
Till Gerlach
Regina Vogelsang
Frank Poplow
Pedro SA GOMES
Agnes Voitl
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Basf Se
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Publication of WO2017060352A1 publication Critical patent/WO2017060352A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature

Definitions

  • the present invention relates to a process for the treatment of waste water resulting from a method for the preparation of a zeolitic material employing an organotemplate as structure directing agent wherein in particular a nonionic adsorbent material is employed to this effect.
  • Zeolites are microporous, typically aluminosilicate minerals and synthetic materials commonly used as commercial adsorbents and catalysts. Zeolites occur naturally but are also produced industrially on a large scale. Although a large number of zeolitic materials may be produced according to methods which allow for the assembly of the regular three-dimensional mi- croporous frameworks found in zeolitic materials according to self-organization mechanisms, a large number of zeolitic materials require the use of structure directing agents for producing the microporous cavities found in such materials. Among structure directing agents employed in the chemical synthesis of zeolitic materials, organic molecules typically referred to as organotem- plates are often employed for creating the unique microporous structures of selected zeolites.
  • zeolitic materials i.e. typically silica and alumina
  • a solvent system typically consists mainly of water for providing a synthesis gel which may then be crystallized at elevated temperatures in a subsequent synthetic reaction process.
  • the solid zeolite product is typically isolated from the reaction mixture by a filtration process accordingly affording an aqueous filtrate containing non- reacted materials as well as secondary products generated during the zeolite synthesis.
  • these may be removed by adsorption and/or ion exchange treatment.
  • Typical adsorbent materials employed to this effect are aluminas, silicates and aluminosilicates as well as carbons and organic polymers.
  • the waste water to be treated is typically contacted with the adsorbent which is usually provided in an adsorption column to this effect.
  • the adsorption capacity of a sorbent material usually increases as temperature decreases (see e.g. Perry's Chemical Engineers Handbook, 8 th edition, Section 16, Figure 16-1 on page 6; N.P. Cheremisinoff, "Handbook of Water and Waste Water Treatment Technologies", Butter- worth-Heinemann 2002, page 41 1 , 2 nd full paragraph).
  • waste water is typically treated at ambient temperature whereas the low adsorption capacity at elevated temperatures is employed in turn for regenerating the adsorbent material such as e.g. by steam treatment thereof (see e.g. Ullmann's Encyclopedia of Industrial Chemistry, Wiley VCH Verlag GmbH & Co., Weinheim 2005, article on "Adsorption", page 49, right column).
  • the present invention relates to a process for the treatment of waste water resulting from a method for the preparation of a zeolitic material employing an organotemplate as structure directing agent, said process comprising:
  • the waste water stream (SO) has a temperature in the range of from 30 to 90°C.
  • the waste water stream (SO) has a temperature in the range of from 30 to 90°C imme- diately before contacting the nonionic adsorbent material in step (3).
  • the specific temperatures which the waste water stream (SO) may have to this effect no particular restrictions apply such that any suitable temperature in the range of from 30 to 90°C may be employed to this effect.
  • the waste water stream (SO) has a temperature in the range of from 35 to 85°C immediately before con- tacting the nonionic adsorbent material in step (3), wherein more preferably the waste water stream (SO) has a temperature in the range of from 40 to 80°C, more preferably of from 45 to 75°C, and more preferably of from 50 to 70°C. According to the present invention it is particularly preferred that the waste water stream (SO) has a temperature in the range of from 55 to 65°C immediately before contacting the nonionic adsorbent material in step (3) of the inventive pro- cess.
  • the temperature of the waste water stream (SO) after having contacted the nonionic adsorbent material in step (3) it is preferred that the temperature thereof is maintained at the same tempera- ture or at a temperature neighboring the temperature of the waste water stream (SO) immediately before contacting the nonionic adsorbent material in step (3).
  • the temperature is maintained in the range of from 30 to 90°C, wherein preferably the temperature of the waste water stream (SO) is maintained at a temperature in the range of from 35 to 85°C during the contacting of the waste water stream with the nonionic adsorbent material.
  • the temperature is maintained in the range of from 40 to 80°C, more preferably of from 45 to 75°C, and more preferably of from 50 to 70°C.
  • the temperature is maintained in the range of from 55 to 65°C.
  • waste water stream (SO) employed in the inventive process
  • the waste water stream (SO) provided in step (1 ) of the in- ventive process and contacted with the nonionic adsorbent material in step (3) thereof may have any suitable pH.
  • the waste water stream (SO) may have a pH ranging anywhere from 2.5 to 12, wherein preferably the waste water stream (SO) has a pH in the range of from 3 to 1 1.5, and more preferably in the range of from 3.5 to 1 1 , more preferably in the range of from 4 to 10.5, more preferably in the range of from 4.5 to 10, more preferably in the range of from 5 to 9.5, more preferably in the range of from 5.5 to 9, and more preferably in the range of from 6 to 8.5.
  • the pH of the waste water stream (SO) is in the range of from 6.5 to 7.5 when it is contacted with the nonionic adsorbent material in step (3).
  • one or more steps are normally performed between the preparation of a zeolitic material employing an organotemplate as a structure directing agent and said step of providing the waste water stream (SO).
  • the resulting zeolitic material is normally removed from the reaction mixture e.g. by filtration and/or centrifugation for obtaining the waste water stream (SO).
  • the reaction mixture obtained from the preparation of a zeolitic material is subject to a treatment with an acid and preferably with a mineral acid which more preferably is nitric acid, wherein said step is performed prior to the preferred step of filtration and/or centrifugation of the zeolitic material for obtaining the mother liquor filtrate provided as waste water stream (SO) in step (1 ) of the inventive process.
  • the zeolitic material may be washed one or more times with distilled water wherein the wash water is preferably added to the initial filtrate for providing the waste water stream (SO).
  • the zeolitic material obtained from either of the aforementioned embodiments is washed one or more times with distilled water and said wash water then directly added to the mother liquor from the reaction mixture for providing the waste water stream (SO) in step (1 ) of the inventive process.
  • SO waste water stream
  • Fur- thermore or alternatively thereto it is preferred that prior to the separation of the zeolitic material from the reaction mixture, said mixture is treated with an acid and preferably with a mineral acid which is particularly preferably nitric acid for precipitation of the zeolitic material.
  • the reaction mixture obtained from the preparation of a zeolitic material is subject to a treatment with an acid and preferably with a mineral acid which more preferably is nitric acid prior to the step of filtration of the zeolitic material for obtaining the mother liquor filtrate provided as waste water stream (SO) in step (1 ) of the inventive process.
  • the mother liquor obtained after separation of the zeolitic material from the reaction mixture obtained from the preparation thereof is not subject to a treatment step prior to being provided as waste water stream (SO).
  • a raw waste water stream is first freed from particulate matter, preferably by filtration and/or sedimentation, wherein it is particu- larly preferred that said raw waste water stream is the reaction mixture directly obtained from the preparation of a zeolitic material employing an organotemplate as structure directing agent which according to preferred embodiments of the present invention is either directly obtained from the reaction or has been only subject to a step of treatment with an acid according to any of the particular and preferred embodiments of the present invention.
  • the raw waste water stream is freed from particulate matter by sedimentation, wherein it is preferred that said sedimentation is achieved with the aid of a settling vessel from which the waste water stream (SO) is obtained as the supernatant.
  • the pH of the waste water stream (SO) provided in step (1 ) may accordingly vary,
  • the pH of the waste water stream (SO) provided in step (1 ) and contacted with the nonionic adsorbent material in step (3) has a pH in the range of from 7 to 13, in particular in the event that the reaction mixture displays a highly basic pH, and that the zeolitic material is washed one or more times with distilled water, the wash water being subsequently added to the waste water stream (SO) for treatment according to the inventive process.
  • the pH of the waste water stream (SO) provided in step (1 ) and contacted with the nonionic adsorbent material in step (3) has a pH in the range of from 7.5 to 12.5, and more preferably from 8 to 12, more preferably from 8.5 to 1 1 .5, and more preferably from 9 to 1 1.
  • the pH of the waste water stream (SO) ranges from 9.5 to 10.5.
  • the pH of the waste water stream (SO) provided in step (1 ) and contacted with the nonionic adsorbent material in step (3) has a pH in the range of from 9 to 14, more preferably from 10 to 13.75, more preferably from 1 1 to 13.5, more preferably from 1 1.5 to 13.25, and more preferably from 12 to 13.
  • the pH of the waste water stream (SO) ranges from 12.25 to 12.75.
  • the nonionic adsorbent material provided in step (2) of the inventive process has a BET surface area in the range of from 200 to 2,000 m 2 /g.
  • BET surface area in the range of from 200 to 2,000 m 2 /g.
  • the BET surface area of the nonionic adsorbent material provided in step (2) may range anywhere from 400 to 1 ,800 m 2 /g, wherein preferably the nonionic adsorbent material has a BET surface area in the range of from 550 to 1 ,600 m 2 /g, more preferably from 650 to 1 ,450 m 2 /g, more preferably from 750 to 1 ,350 m 2 /g, and more preferably from 850 to 1 ,150 m 2 /g.
  • the nonionic adsorbent material provided in step (2) has a BET surface area in the range of from 950 to 1 ,050 m 2 /g.
  • the method employed for determining the BET surface area of a given nonionic adsorbent material there is no particular restriction as to the method employed for determining the BET surface area of a given nonionic adsorbent material provided that the values obtained conform with the particular and preferred ranges of values as defined in the present application. It is, however preferred that the values expressed in the present application relative to the BET surface area of the nonionic adsorbent material refer to values determined according to ISO 9277 or DIN 66131 , wherein it is preferred according to the present invention that the BET surface area of the nonionic adsorbent material refers to values obtained according to ISO 9277.
  • the nonionic adsorbent material is employed in the inventive process
  • the nonionic adsorbent material is provided in the form of a powder and/or granulate, preferably in the form of a granulate.
  • the preferred powders and/or granulates of the nonionic adsorbent materials employed in the inventive process again no particular restrictions apply neither with respect to the size nor with respect to the dimensions of the particles employed to this effect.
  • the nonionic adsorbent material used in the form of a powder and/or granulate preferably in the form of a granulate, displays an particle size D90 in the range of from 0.5 to 5 mm, and more preferably of from 1.0 to 4 mm, more preferably of from 1.3 to 3 mm, more preferably of from 1 .5 to 2.7 mm, more preferably of from 1.7 to 2.4 mm, and more preferably of from 1.8 to 2.2 mm.
  • the nonionic adsorbent material displays an particle size D90 in the range of from 1.9 to 2.1 mm.
  • the term "granulate” generally refers to a conglom- eration of discrete solid, macroscopic particles characterized by a loss of energy whenever the particles interact (the most common example would be friction when grains collide).
  • the nonionic adsorbent material when used in the form of a powder and/or granulate, preferably in the form of a granulate displays a particle size D50 in the range of from 0.2 to 0.7 mm, and more preferably of from 0.3 to 0.6 mm, more preferably of from 0.35 to 0.55 mm, more preferably of from 0.38 to 0.5 mm, and more preferably of from 0.4 to 0.47 mm.
  • the nonionic adsorbent material when used in the form of a powder and/or granulate, preferably in the form of a granulate displays a particle size D50 in the range of from 0.42 to 0.44 mm.
  • the values for the particle size D90 and for the average particle size D50 as defined in the present application in principle, no particular restrictions apply relative to the method according to which these are determined. Furthermore, said values may refer either to the particle size distribution by volume or by number. It is, however, preferred according to the present in- vention that the values for the particle size D90 and for the average particle size D50 as defined according to particular and preferred embodiments of the present invention refer to the particle size D90 and to the average particle size D50 by volume. Furthermore and independently thereof, it is preferred according to the present invention that the values for the particle size D90 and the average particle size D50 are obtained according to ISO 13320:2009, wherein the parti- cle size analysis is performed by laser diffraction methods.
  • the nonionic adsorbent material is provided in step (2) for contacting with the waste water stream (SO) in step (3)
  • the nonionic adsorbent material may be provided in any form such as in the form of a shaped body as obtained from sintering or extrusion of the material, if necessary in the presence of a binder or other material for enabling the adhesion within the shaped body.
  • the nonionic adsorbent material may however also be provided, in addition to or as an alternative to the foregoing shaped bodies, in particu- late form such as in the form of a powder and/or granulate, preferably in the form of a granulate.
  • the nonionic adsorbent material is provided in particulate from and in particular in the form of a powder and/or granulate, preferably in the form of a granulate, it is preferred that said powder and/or granulate is provided in packed form such as for example in the form of packed columns for achieving a greater bulk dry density than in the loose material.
  • the bulk dry density of the nonionic adsorbent material provided in step (2) prior to the contacting thereof with the waste water stream (SO) in step (3) ranges from 200 to 700 g/L, and more preferably from 210 to 600 g/L, more preferably from 230 to 500 g/L, more preferably from 250 to 450 g/L, more preferably from 270 to 400 g/L, and more preferably from 280 to 350 g/L.
  • the bulk dry density of the nonionic adsorbent material provided in step (2) according to any of the particular and preferred embodiments as defined in the present application prior to the contacting thereof with the waste water stream (SO) in step (3) ranges from 290 to 320 g/L.
  • the nonionic adsorbent material employed in the inventive process no particular restrictions apply with respect to the materials and compounds which may be employed to this effect provided that these do not display ionic bonding as typically found in metal or metalloid salts as well as in metal or metalloid oxides.
  • the nonionic adsorbent material comprises and preferably consists of non-metals and/or non-metal compounds displaying covalent bonding between their constituent atoms.
  • nonionic adsorbent materials according to the present invention exclude the presence of ionic adsorbent materials therein such as silica, alumina, silicates or alu- minosilicates.
  • the nonionic adsorbent material provided in step (2) and contacted with the waste water stream (SO) in step (3) comprises and preferably consists of one or more compounds selected from the group consisting of carbon- based compounds.
  • the preferred carbon-based compounds comprised in the nonionic adsorbent material or which the nonionic adsorbent material consists of there is no particular restriction as to which carbon-based compounds may be employed to this effect provided that these are nonionic.
  • the nonionic adsorbent material preferably comprises and more preferably consists of one or more compounds selected from the group consisting of polymers, activated carbon, and mixtures of two or more thereof, and more preferably from the group consisting of activated carbon, polystyrenes, polyacrylates, phenolic resins, phenolic amine resins, polydivinylbenzene, and mixtures thereof, and more preferably from the group consisting of activated carbon, polystyrene, polyacrylate, phenolic resin, phenolic amine resin, polydivinylbenzene, and mixtures thereof.
  • the nonionic adsorbent material provided in step (2) and contacted with the waste water stream (SO) in step (3) comprises activated carbon, wherein more preferably the nonionic adsorbent material is activated carbon.
  • the activated carbon employed as nonionic adsorbent material according to particu- lar and preferred embodiments of the present invention, no particular restrictions apply as to the source from which said activated carbon is obtained, such that it may for example be shell- based, wood-based, petroleum-based, peat-based, lignite-based, bituminous-coal-based, and/or synthetic polymer-based, i.e. obtained from pyrolysis of synthetic polymers.
  • the organotemplate which may be employed as structure directing agent in the inventive process, again no particular restrictions apply provided that it comprises an organic compound and in particular a carbon-based compound and/or a salt thereof.
  • the organotemplate employed in the present invention as structure directing agent in the inventive process may be selected from the group consisting of N-alkyl-3-quinuclidinol com- pounds, ⁇ , ⁇ , ⁇ -trialkyl-exoaminonorbornane compounds, N,N,N-trimethyl-1-adamantylam- monium compounds, N,N,N-trimethyl-2-adamantylammonium compounds, ⁇ , ⁇ , ⁇ -trimethyl- cyclohexylammonium compounds, N,N-dimethyl-3,3-dimethylpiperidinium compounds, N,N- methylethyl-3,3-dimethylpiperidinium compounds, N,N-dimethyl-2-methylpiperidinium com- pounds, 1 , 3,3,6, 6-pentamethyl-6-azonio-bicyclo(3.2.1 )octane compounds, N,N-dimethylcyc- lohexylamine compounds,
  • the organotemplate employed as structure directing agent for the preparation of a zeolitic material in the inventive process comprises N,N,N-trimethyl-1 -adamantylammonium and/or N,N,N-trimethyl-2-adamantylam- monium hydroxide, preferably N,N,N-trimethyl-1 -adamantylammonium.
  • the inventive treatment process leading to the removal of organic waste from the waste water stream (SO) besides removing the organotemplate as such from the waste water, the inventive process also allows for the removal of degradation products of the organotemplate typically found in the waste water resulting from the preparation of a zeolitic material.
  • organotemplate degradation products which may be contained in the waste water stream (SO) provided in step (1 )
  • no particular restrictions apply such that any conceivable deg- radation product may be contained therein depending on the conditions of the preparation of the zeolitic material which according to the present invention are not in any way restricted provided that a zeolitic material is obtained from the preparation method.
  • the organotemplate degradation product may comprise one or more compounds selected from the group consisting of trialkylamines, tetraalkylammonium hydroxides, 1-adamantol, 2-adamantol, and mixtures of two or more thereof, wherein preferably the organotemplate degradation product which may be comprised in the waste water provided is step (1 ) of the inventive process is preferably selected from the group consisting of tri(C1-C5)alkylamines, tetra(C1 - C5)alkylammonium hydroxides, 1-adamantol, 2-adamantol, and mixtures of two or more thereof, more preferably from the group consisting of tri(C1-C4)alkylamines, tetra(C1 - C4)alkylammonium hydroxides, 1-adamantol, 2-adamantol, and mixtures of two or more thereof, more preferably from the group consisting of tri(C1-C3)alkylamines,
  • the organotemplate degradation product which may be contained in the waste water stream (SO) provided in step (1 ) is 1 -adamantol and/or 2-adamantol, wherein more preferably the organotemplate degradation product is 1 -adamantol.
  • the concentration of the organotemplate and/or of the organotemplate degradation product in the waste water stream (SO) provided in step (1 ) of the inventive process no particular restrictions apply such that in principle any conceivable concentration of the organotemplate and/or of the organotemplate degradation product may be contained therein.
  • the concentration of the organotemplate in the waste water stream (SO) may range anywhere from 50 to 3,000 ppmw, wherein preferably the concentration of the organotemplate ranges from 100 to 2,000 ppmw, more preferably of from 200 to 1 ,500 ppmw, more preferably from 300 to 1 ,000 ppmw, more preferably of from 350 to 800 ppmw, and more preferably of from 400 to 600 ppmw.
  • the concentration of the organotemplate in the waste water stream (SO) provided in step (1 ) is in the range of from 450 to 550 ppmw.
  • the organotemplate degradation product in the waste water stream (SO) such that its concentration may for example range anywhere from 10 to 3,000 ppmw, wherein it is preferred that the concentration of the organotemplate degradation product ranges from 200 to 2,000 ppmw, more preferably of from 300 to 1 ,500 ppmw, more preferably of from 400 to 1 ,200 ppmw, more preferably of from 450 to 900 ppmw, and more preferably of from 500 to 700 ppmw.
  • the concentration of the organotemplate degradation product in the waste water stream (SO) provided in step (1 ) is in the range of from 550 to 650 ppmw.
  • ppmw as employed in the present application, said term stands for parts per million by weight.
  • the waste water stream (SO) may further comprise one or more alcohols wherein preferably the one or more alcohols are selected from the group of optionally substituted, branched and/or unbranched C1-C4 alcohols, and more preferably from the group consisting of optionally substituted, branched and/or unbranched C2-C3 alcohols.
  • the waste water stream (SO) further comprises one or more alcohols selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, and mixtures of two or more thereof, and more preferably from the group consisting of methanol, ethanol, isopropanol, and mixtures of two or more thereof.
  • the waste water stream (SO) further comprises isopropanol as the one or more alcohols.
  • the one or more alcohols may be contained in the waste water stream (SO) in an amount ranging anywhere from 0.01 to 50 g/L, wherein preferably the one or more alcohols are con- tained in the waste water stream (SO) in an amount ranging from 0.05 to 40 g/L, more preferably from 0.1 to 30 g/L, more preferably from 0.5 to 27 g/L, more preferably from 1 to 25 g/L, more preferably from 5 to 22 g/L, more preferably from 10 to 20 g/L, and more preferably from 12 to 18 g/L.
  • the one or more alcohols are contained in the waste water stream (SO) in an amount ranging from 14 to 16 g
  • inventive process may be conducted in a continuous mode as well as in a batch mode or also as a combination of a continuous and of a batch mode. It is, however, preferred according to the present invention that the inventive process is conducted in a continuous mode, in particular with respect to steps (3) and (4) defined therein.
  • the nonionic adsorbent material in step (2) is provided in at least one adsorption column and preferably in two or more adsorption columns for contacting with the waste water stream (SO) in step (3).
  • the nonionic adsorbent material in step (2) is provided in two to four adsorption columns, more preferably in two or three adsorption columns, and more preferably in two adsorption columns.
  • each of the one or more adsorption columns may respectively contain anywhere from 100 to 20,000 kg of the nonionic ad- sorbent material.
  • each of the one or more adsorption columns respectively contain from 500 to 18,000 kg of the nonionic adsorbent material, more preferably from 1 ,000 to 16,000 kg, more preferably from 3,000 to 14,000 kg, more preferably from 5,000 to 12,000 kg, more preferably from 6,000 to 10,000 kg, and more preferably from 7,000 to 9,000 kg.
  • the one or more adsorption columns respectively contain from 7,500 to 8,500 kg of the nonionic adsorbent material.
  • each of the one or more adsorption columns may respectively display a diameter anywhere in the range of from 0.5 to 8 m, wherein it is preferred according to the inventive process that each of the one or more adsorption columns respectively display a diameter in the range of from 1 to 5 m, and more preferably of from 1 .5 to 3 m, more preferably from 2 to 2.7 m, and more preferably from 2.2 to 2.5 m. According to the present invention it is particularly preferred that each of the one or more adsorption columns respectively display a diameter in the range of from 2.3 to 2.4 m.
  • each of the one or more adsorption columns are respectively packed bed adsorption columns, wherein the height of the nonionic adsorbent bed in the one or more adsorption columns may range anywhere from 2 to 10 m, wherein preferably the height of the nonionic adsorbent bed in each of the one or more adsorption columns ranges from 3 to 8 m, and more preferably from 3.5 to 6 m, more preferably from 3.8 to 5.5 m, more preferably from 4 to 5 m, and more preferably from 4.2 to 4.8 m.
  • the one or more adsorption columns are respectively packed bed adsorption columns wherein the height of the nonionic adsorbent bed in each of the one or more adsorption columns ranges from 4.4 to 4.6 m.
  • the specific type of adsorption columns which may be employed in the particular and preferred embodiments of the present invention, no particular restrictions apply such that any suitable type of adsorption columns may be used to this effect. It is, however, preferred according to the present invention that the temperature of the one or more adsorption columns may be regulated during the course of the inventive process, and in particular may be maintained at a specific temperature.
  • the one or more adsorption columns are each respectively double wall adsorption columns of which the temperature may be regulated during the process of the treatment of the waste water stream (SO).
  • the temperature of each of the one or more double wall columns is respectively maintained at a temperature in the range of from 30 to 90°C, and preferably from 35 to 85°C, more preferably from 40 to 80°C, more preferably from 45 to 75°C, and more preferably of from 50 to 70°C.
  • step (3) the temperature of the one or more double wall columns in step (3) is respectively maintained at a temperature in the range of from 55 to 65°C.
  • step (4) of the inventive process the treated waste water obtained from step (3) is separated from the nonionic adsorbent material for obtaining a treated waste water stream (S1 ).
  • separation in step (4) is preferably achieved by filtration and/or centrifugation, wherein more preferably the separation of the treated waste water from the nonionic adsorbent material in step (4) is achieved by filtration.
  • the nonionic adsorbent material eventually becomes saturated with organic waste such that its adsorption capacity is diminished. As a result, it is necessary to replace and/or regenerate the nonionic adsorbent material. To this effect, no particular restrictions apply according to the present invention such that any suitable method for the regeneration of the nonionic adsorbent material may be employed. It is, however, preferred according to the present invention that the regeneration of the nonionic adsorbent material is achieved with the aid of steam. Therefore, it is preferred according to the present invention that the process further includes a step of
  • the process further includes a step of regenerating the nonionic adsorbent material with steam.
  • the steam employed for the preferred regeneration of the nonionic adsorbent material may range anywhere from 100 to 160°C, wherein preferably prior to contacting the nonionic adsorbent material, the steam has a temperature in the range of from 105 to 140°C, more preferably from 1 10 to 130°C, and more preferably from 1 15 to 125°C.
  • the present invention is further characterized by the following and particular preferred embodi- ments, including the combination and embodiments indicated by the respective dependencies:
  • the waste water stream (SO) has a temperature in the range of from 30 to 90°C.
  • the waste water stream (SO) has a temperature in the range of from 35 to 85°C, preferably of from 40 to 80°C, more preferably of from 45 to 75°C, more preferably of from 50 to 70°C, and more preferably of from 55 to 65°C.
  • the waste water stream (SO) has a pH in the range of from 2.5 to 12, preferably in the range of from 3 to 1 1 .5, more preferably in the range of from 3.5 to 1 1 , more preferably in the range of from 4 to 10.5, more preferably in the range of from 4.5 to 10, more preferably in the range of from 5 to 9.5, more preferably in the range of from 5.5 to 9, more preferably in the range of from 6 to 8.5, and more preferably in the range of from 6.5 to 7.5.
  • the nonionic adsorbent material has a BET surface area in the range of from 400 to 1 ,800 m 2 /g, preferably from 550 to 1 ,600 m 2 /g, more preferably from 650 to 1 ,450 m 2 /g, more preferably from 750 to 1 ,350 m 2 /g, more preferably from 850 to 1 ,150 m 2 /g, and more preferably from 950 to 1 ,050 m 2 /g, wherein preferably, the BET surface are of the nonionic adsorbent material is determined according to ISO 9277 or DIN 66131 , more preferably according to ISO 9277.
  • any of embodiments 1 to 7, wherein the bulk dry density of the nonionic adsorbent material provided in (2) prior to the contacting thereof with the waste water stream (SO) in (3) ranges from 200 to 700 g/L, preferably from 210 to 600 g/L, more preferably from 230 to 500 g/L, more preferably from 250 to 450 g/L, more preferably from 270 to 400 g/L, more preferably from 280 to 350 g/L, and more preferably from 290 to 320 g/L.
  • the nonionic adsorbent material comprises one or more compounds selected from the group consisting of carbon-based compounds, preferably from the group consisting of polymers, activated carbon, and mixtures of two or more thereof, more preferably from the group consisting of activated carbon, polystyrenes, polyacrylates, phenolic resins, phenolic amine resins, polydivinylbenzene, and mixtures thereof, more preferably from the group consisting of activated carbon, polystyrene, polyacrylate, phenolic resin, phenolic amine resin, polydivinylbenzene, and mixtures thereof, wherein more preferably the nonionic adsorbent material comprises activated carbon, wherein more preferably the nonionic adsorbent material is activated carbon.
  • organotemplate is selected from the group consisting of N-alkyl-3-quinuclidinol compounds, ⁇ , ⁇ , ⁇ -trialkyl- exoaminonorbornane compounds, N,N,N-trimethyl-1 -adamantylammonium compounds, N,N,N-trimethyl-2-adamantylammonium compounds, ⁇ , ⁇ , ⁇ -trimethyl- cyclohexylammonium compounds, N,N-dimethyl-3,3-dimethylpiperidinium compounds, N,N-methylethyl-3,3-dimethylpiperidinium compounds, N,N-dimethyl-2-methylpiperidinium compounds, 1 , 3,3,6, 6-pentamethyl-6-azonio-bicyclo(3.2.1 )octane compounds, N,N- dimethylcyclohexylamine compounds, ⁇ , ⁇ , ⁇ -trimethylbenzylammonium compounds, and mixtures of two
  • the organotemplate comprises N,N,N-trimethyl-1 - adamantylammonium and/or N,N,N-trimethyl-2-adamantylammonium hydroxide, wherein more preferably the organotemplate is N,N,N-trimethyl-1 -adamantylammonium and/or N,N,N-trimethyl-2-adamantylammonium hydroxide, preferably N,N,N-trimethyl-1- adamantylammonium.
  • organotemplate degradation product is selected from the group consisting of trialkylamines, tetraalkylammonium hydroxides, 1 -adamantol, 2-adamantol, and mixtures of two or more thereof, preferably from the group consisting of tri(C1-C5)alkylamines, tetra(C1-C5)alkylammonium hydroxides, 1 - adamantol, 2-adamantol, and mixtures of two or more thereof, more preferably from the group consisting of tri(C1 -C4)alkylamines, tetra(C1-C4)alkylammonium hydroxides, 1- adamantol, 2-adamantol, and mixtures of two or more thereof, more preferably from the group consisting of tri(C1 -C3)alkylamines, tetra(C1-C3)alkylammonium hydroxides, 1-
  • concentration of the organotem- plate in the waste water stream (SO) is in the range of from 50 to 3,000 ppmw, preferably of from 100 to 2,000 ppmw, more preferably of from 200 to 1 ,500 ppmw, more preferably of from 300 to 1 ,000 ppmw, more preferably of from 350 to 800 ppmw, more preferably of from 400 to 600 ppmw, and more preferably of from 450 to 550 ppmw.
  • 3,000 ppmw preferably of from 200 to 2,000 ppmw, more preferably of from 300 to 1 ,500 ppmw, more preferably of from 400 to 1 ,200 ppmw, more preferably of from 450 to 900 ppmw, more preferably of from 500 to 700 ppmw, and more preferably of from 550 to 650 ppmw. 14.
  • the waste water stream (SO) further comprises one or more alcohols, preferably one or more alcohols selected from the group of optionally substituted, branched and/or unbranched C1 -C4 alcohols, more preferably from the group consisting of optionally substituted, branched and/or unbranched C2-C3 alcohols, more preferably from the group consisting of methanol, ethanol, n-propanol, iso- propanol, n-butanol, and mixtures of two or more thereof, more preferably from the group consisting of methanol, ethanol, isopropanol, and mixtures of two or more thereof, wherein more preferably isopropanol is further in the waste water stream (SO).
  • one or more alcohols selected from the group of optionally substituted, branched and/or unbranched C1 -C4 alcohols more preferably from the group consisting of optionally substituted, branched and/or unbranched C2-C3 alcohols, more preferably from the group consisting
  • the one or more adsorption columns respectively contain from 100 to 20,000 kg of the nonionic adsorbent material, more preferably from 500 to 18,000 kg, more preferably from 1 ,000 to 16,000 kg, more preferably from 3,000 to 14,000 kg, more preferably from 5,000 to 12,000 kg, more preferably from 6,000 to 10,000 kg, more preferably from 7,000 to 9,000 kg, and more preferably from 7,500 to 8,500 kg.
  • a raw waste water stream is first freed from particulate matter, preferably by filtration and/or sedimentation, more preferably by sedimentation, wherein more preferably sedimentation is achieved with the aid of a settling vessel from which the waste water stream (SO) is obtained as the supernatant.
  • the steam has a temperature in the range of from 100 to 160°C, preferably from 105 to 140°C, more preferably from 1 10 to 130°C, and more preferably from 1 15 to 125°C.
  • the model waste solutions used in the experiments were mixed from the pure components. To this effect, deionized water was employed, to which the additives adamantyltrimethylammonium hydroxide (ATMAOH), adamantol, trimethylamine (TMA) and tetramethylammonium hydroxide (TMAOH), respectively, were added.
  • the additives adamantyltrimethylammonium- hydroxide and tetramethylammonium hydroxide (TMAOH) are representative of organotem- plates employed in the synthesis of zeolites, whereas adamantol and trimethylamine are typical degradation products of the aforementioned organotemplates.
  • the evaluated activated carbon absorbents included CarboTech Pool W 1-3 (CarboTech AC GmbH), CarboTech CGF 12x40/85 (CarboTech AC GmbH), Cyclecarb® 201 (Calgon Carbon Corp.), and Cyclecarb® 301 (Calgon Carbon Corp.).
  • the clay-based adsorbent F24 (BASF) as the ion-exchange resin material Amberlite® 252 H (Rohm and Haas) were employed in the comparative examples respectively.
  • a product sample and a weighed amount of adsorbent was treated in the shaking cabinet at a constant temperature for up to 72 h for achieving an equilibrium between the solid and liquid phase.
  • Comparative Example 1 Shaking flask experiments with a trimethylamine / 1-adamantol / water mixture at 20 °C
  • TMA is entirely removed using the ion-exchange resin (Amberlite®), wherein the removal capacity using a clay-based sorbent (F24) is poor.
  • the samples employing activated carbon performed even worse that the clay-based sorbent, only displaying a notable removal capacity when employed at higher concentration. The tendency, however, is reversed in the case of adamantol, which is well removed using activated carbon compared to the aforementioned clay-based sorbent and ion-exchange resin, which display no notable removal capacity with respect to adamantol.
  • Example 1 Shaking flask experiments with a trimethylamine / 1 -adamantol / water mixture at 40°C
  • Comparative Example 1 was repeated, yet the flasks which were placed in a shaking cabinet for 72 hours at a constant temperature of 20°C. As in Example 1 , the samples were subsequently filtered, and the amount of adamantol and trymethylamine remaining in the supernatant respectively determined. The amounts of model waste water solution and sorbent as well as the results from analysis of the supernatant after filtration are indicated in Table 2 below.
  • Example 2 Shaking flask experiments with a trimethylamine / 1 -adamantol / water mixture at 60°C
  • Comparative Example 2 was repeated, wherein the shaking cabinet was held at a constant temperature of 60°C.
  • the amounts of model waste water solution and sorbent as well as the results from analysis of the supernatant after filtration are indicated in Table 3 below.
  • Example 3 Shaking flask experiments with trimethylamine / 1 -adamantol / trimethylammonium hydroxide / 1 -adamantyltrimethylammonium hydroxide / water mixture at 60°C
  • a model waste water solution 981.6 g deionized water, 15 g isopropa- nol (15000 ppmw)
  • 0.4 g of tetramethylammonium hydroxide (TMAOH) (25% aqueous solution; 100 ppmw)
  • 2 g trimethylamine 25% aqueous solution; 500 ppmw
  • 0.5 g 1 - adamantol (500 ppmw) were admixed.
  • the solution was then placed in a sonicator for 4 h at 50°C in view of the poor solubility of adamantol in water, after which the solution was filtered through a folded filter for removing remaining solid components. Portions of the solution were respectively combined with sorbent materials in respective flasks which were then placed in a shaking cabinet operating at a rate of 165 rotations per minute for 70.5 hours at a constant temperature of 60°C. Subsequently, the samples were filtered, and the amount of 1 -adamantol, trimethylamine, 1-adamantyltrimethylammonium hydroxide, and tetramethylammonium hydrox- ide remaining in the supernatant respectively determined.
  • waste water solutions from the production of zeolitic materials which are normally obtained at elevated tempera- tures may actually directly be treated without leading to loss in treatment eff.
  • the sorption efficiency may actually be increased when the treatment of the waste water with a nonionic sorbent such as activated carbon is performed at elevated temperatures. Therefore, a highly efficient process for the treatment of waste water resulting from the preparation of zeolitic materials is obtained according to the present inven- tion.

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Abstract

La présente invention concerne un procédé pour le traitement d'eaux usées résultant d'un procédé de préparation d'un matériau zéolitique utilisant une matrice organique en tant qu'agent d'orientation de structure, ledit procédé consistant à : (1) fournir un flux d'eaux usées (S0) comprenant de l'eau et une matrice organique et/ou un produit de dégradation de matrice organique (2); fournir un matériau adsorbant non ionique ayant une aire de surface BET allant de 200 à 2 000 m2/g; (3) mettre en contact le flux d'eaux usées (S0) avec le matériau adsorbant non ionique; et (4) séparer les eaux usées traitées du matériau adsorbant non ionique afin d'obtenir un flux d'eaux usées traitées (S1); immédiatement avant d'entrer en contact avec le matériau adsorbant non ionique dans l'étape (3), le flux d'eaux usées (S0) ayant une température comprise entre 30 et 90° C.
PCT/EP2016/073878 2015-10-08 2016-10-06 Procédé pour le traitement d'eaux usées contenant une matrice organique résultant de la synthèse de zéolite WO2017060352A1 (fr)

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US11203566B2 (en) 2017-07-05 2021-12-21 Basf Se Hydrogenation of aromatic compounds
CN114477653A (zh) * 2022-02-24 2022-05-13 陕西煤业化工技术研究院有限责任公司 一种分子筛生产过程废水处理方法及系统

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US11203566B2 (en) 2017-07-05 2021-12-21 Basf Se Hydrogenation of aromatic compounds
CN114477653A (zh) * 2022-02-24 2022-05-13 陕西煤业化工技术研究院有限责任公司 一种分子筛生产过程废水处理方法及系统
CN114477653B (zh) * 2022-02-24 2023-06-02 陕西煤业化工技术研究院有限责任公司 一种分子筛生产过程废水处理方法及系统

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